Synthetic resinous material and method of producing it



Patented June 21, 1938 UNITED STATES PATENT orrlcc Irvin W. Humphrey,Wilmington, Del., assignor to Hercules Powder Company,

Wilmington,

Del, a corporation of Delaware No Drawing.

Application ahliay 14, 1935,

Serial No. 21.3

10 Claims. (01. zoo-99.40)

This invention relates to a new resinous material and method ofproducing.

In accordance with the method embodying this invention maleic anhydrideis reacted with a re- 10 compound reaction product. the unsaturation ofwhich is reduced by hydrogen and which contains a rosin acid radical anda reactive anhydride group derived from the maleic dride.

15 In carrying out the method in accordance with this invention for theproduction ofprodnets in accordance therewith, maleic acid may be usedin place of maleic anhydride, since it will be converted into maleicanhydride at the reaction a temperature. The reactive rosin compoundwill comprise rosin, refined or unrefined, rosin esters, rosin oil,abietyl alcohol, and the like compounds containing unsaturated bondstypical oi. rosin acids, such as abietic acid, pimaric acid, and the 25like. By virtue of possessing a reactive anhydride group, the variousresinous products in accordance with this invention maybereacted with analkali, as-sodium hydroxide, calcium hydroxide, so potassium carbonate,etc., or with a reactive oxide as calcium oxide, ethylene oxide, etc.,or with a suitable alcohol such as methanol, ethyl, butyl, amyl, propyl,hydroabietyl, cyclohexanol, benzyl,

anhyoleyl, tetrahydrofurfuryl, stearol, laurel, a glycol,

at as ethylene, butylene, propylene, or diethylene, glycol, gycerol,borneol, fenchyl, pentaerythrite, ethylene glycol monoethyl ether,sorbital, or mixtures thereof, etc.

The products in accordance with this invention ill will be adaptable foruse in protective coatings such as lacquers, varnishes, etc., but forsuch use are preferably first converted into one of their more complexesters, by treatment with a polyhydric alcohol, such as ethylene glycolor glycerol.

45 An excess of the polyhydric alcohol may be used over that required tocombine with the anhydride group and any free hydroxyl groups thusintroduced may be esterifled by treatment with an organic acid such asacetic, citric, succinic, 5 phthalic, abietic, dihydro or tetrohydroabietic, oleic, linoleic, butyric, propionic, linolenic, stearic,sebacic pimaric adipic, furoic, terpinene-maleic anhydride,pinene-maleie anhydride, butadienemaleic anhydride, etc. or mixtures ofsuitable or- 55 ganlc acids, yielding a product which is also adaptedfor 'use in protective coatings and in plastics. Drying or semi-dryingoils may be used to modify the product, if desired.

The method in accordance with this invention for production of the newresinous materials embodying this invention and the character of thematerial will appear in greater detail from the following descriptionand examples."

For the production of the composition embodying this invention, maleicanhydride may be reacted with rosin or a rosin acid, as, for example,abietic acid, primaric acid, or the like, with a rosin or rosin acidester, as an ester of a monohydric or. polyhydric alcohol, as, forexample, ethyl abietate, methyl abietate, propyl abietate, bornylabietate, tetrahydrofurfuryl abietate, lauryl abietate, stearylabietate, hydroabietyl abietate, butyl abietate, amyl abietate, a glycolabietate, glycerol abietate, benzyl abietate, cyclohexanol abietate,ethylene glycol monobutyl abietate, phenyl abietate, etc., with aninorganic abietate as, for example, sodium, calcium, aluminum abietates,etc. with rosin oil, abietyl alcohol, or other reactive rosin compoundcontaining unsaturated bonds typical of rosin acids.

, The time required for effecting the reaction between maleic anhydrideand a rosin compound of the type indicated will vary with thetemperature used and the reactivity of the particular rosin compoundinvolved. Generally speaking, to, with a temperature of about C. toabout 250 0., or higher, the reaction will require from about one toabout fifteen hours. 'Where the rosin compound comprises abietlc acid orone of its derivatives, the reaction will be effected at a astemperature of about 125 C. to about C. in a period of about two toabouttenhours.

If desired, a catalyst may be used to facilitate the reaction. By way ofexample, paratoluene sulphonic acid, benzene sulphonic acid, or other 0suitable catalyst may be used.

For effecting the hydrogenation of the reaction product the reactionproduct will be subjected to treatment by contacting, in a molten state,or in solutiqn in a suitable solvent, as, for example, 4,5 ethylacetate, butyl acetate, toluene, etc., with hydrogen in the presenceofja hydrogenation catalyst under variousconditions of pressure andtemperature, depending upon the particular reaction product treated, thesolvent used and the 5 I type and activity of the hydrogenation catalystused. Generally speaking, where a base metal catalyst, as nickel,nickel-copper, cobalt, or mixtures thereof, is used the treatment willbe at a temperature of about 125 C. to about 225.C.,

unara hydrogen pressure of about 200 lbs. to. about 15,000 lbs., orwithin the narrower range about 1500 lbs. to about 5,000 lbs., and for aperiod of about A to about 2 hours. when a noble metal catalyst, asplatinum, palladium, or the like, is used, a temperature of about C. toabout 50 C. and a hydrogen pressure down to atmospheric will be'foundeifective.

Thus, broadly speaking, procedure in accordance with this invention willcomprise the formation of a product of the reaction of maleic anhydrideand a reactive rosin compound having unsaturated bonds typical of rosinacids, as abietic, pimaric and the like, and hydrogenating the productby treatment thereof with hydrogen under suitable conditions asindicated.

As illustrative of the preparation of a resinous material embodying thisinvention in accordance with the method embodying this invention, forexample, 82 grams of technical ethyl abietate are heated with grams ofmaleic anhydride at a temperature of 170 C. for eight hours. Thereaction product may then be partially distilled at a temperature ofabout 225 C.-250 C. under about 5-10 Hg. mm. pressure to remove anyunreacted ethyl abietate and maleic anhydride. The product will amountto about 85 grams of resinous material slightly softer than rosin,having an acid number of about 130 and a saponiilcation number of about250. The resinous product will be fairly pale in color and can be partlydistilled under about 5 mm, pressure using a bath temperature of about250 C. to 300 C.

The product is then melted by heat, or dissolved in a suitable solventsuch as, for example, butyl acetate, to a concentration of 20%, and apowdered nickel catalyst added to the. solution in the amount of 2%.Hydrogen is then agitated with the solution at a temperature of about160 C. to about 190 C. and under a hydrogen pressure of. about 2500 lbs.to about 2800 lbs. until the, absorption of hydrogen practically ceases.The product will then be separated from the catalyst, by filtration, andrecovered from solution, if treated in solution, by evaporation oi! oithe solvent.

As a further illustration, for example, 80 parts of glycerol abietate,A. N. 5.8, thiocyanate value 72.8, are heated with parts of maleicanhydride at 170 C. for 6 hours. Distilling oil the nonreacted maleicanhydride will leave a hard resinous product, A. N. 184, S. N. about220, thiocyanate value 1.6.

The product is then dissolved in, for example, ethyl acetate to aconcentration of about 15%, and, in admixture with a powdered nickelcatalyst, agitated with hydrogen at a temperature of about 210 C.-220 C.and under a hydrogen pressure of about 4,000-4,500 lbs.

As further illustrative, 224 parts of rosin oil are reacted with 56parts of maleic anhydride by heating at about 170 C. for six hours. Thereaction product is then treated at a temperature of about 225 C. andunder a pressure of about 5 mm. mercury to distil of! unreacted rosinoil. The distillate may amount to as much as one-half of the originalrosin oil, depending upon the acidity, method of production, etc., ofthe rosin oil. The product in solution is then hydrogenated by treatmentwith hydrogen in the presence of, for example, a platinum catalyst, at atemperature of about C. and under 15 lbs. hydrogen pressure, and finallyseparated from the catalyst and solventif in solution.

As a further illustration, for example, 160 parts of abietic acid orrosin and 54 parts of maleic anhydride are admixed and heated at atemperature of say 170 C. for say about three hours. The heating isdesirably carried out in a bath On completion of the heating for aboutthree hours, the temperature of the bath may be desirably raised toabout 250 C. and the pressure on the reaction mass reduced say to apressure of about 5 mm. mercury in orderto remove small amounts of freemaleic anhydride.

The reaction product will be hydrogenated, for example, by contactinghydrogen with a solution thereof in toluene, at a temperature of about.

l-200 C. and under a hydrogen pressure of about 2000-2200 lbs., in thepresence of a powdered nickel catalyst which should be mixed with thesolution. On completion of the hydrogenation the catalyst will befiltered out and the hydrogenated product recovered by distilling of!the solvent.

Various other rosin compounds, as abietyl alcohol, abietic anhydride,etc. may be reacted with maleic anhydride and the hydrogenation thereofwill be eifected as described above with the use of rosin oil, rosinesters and rosin.

Generally about one mol. of maleic anhydride will be used per mol. of anabietic acid ester, if the latter is derived from a monohydric alcohol.but the molar proportion of the anhydride may range about 0.8 to 1.2,depending chieiiy upon the reactivity of the isomers present in theabietic acid ester. In event the ester is a diabietate it will normallyrequire twice as much maleic an hydride, while a triabietate willusually take three times as much anhydride per mol. as a monoabietate.

In proceeding for the preparation of the product, the maleic anhydrideand the rosin compound may be reacted in solution in a suitable solvent,as, for example, xylene, tetralin, chlorbenzene, etc. Where the reactionis effected in the presence of a solvent the above procedure may befollowed and the product, after the reaction has been effected,separated from ,the solvent by distillation.

Compositions in accordance with this invention, as has been indicated,may be formed by reacting various reactive rosin compounds havingunsaturated reactive bonds typical of rosin acids with maleic anhydridefollowing the procedure exemplified.

The hydrogenated product may, if desired, be neutralized with analcohol, as for example, a monohydric alcohol or a polyhydric alcoholand, if desired, though not necessarily, the alcohol treated product maybe subjected to treatment with, for example, an organic acid to effecteaterification of any free hydroxyl groups introduced as a result oftreatment with an excess of alcohol. In connection with treatment of thehydrogenated reaction product with an alcohol, an esterificationcatalyst, as for example, toluene sulphonic acid, sulphuric acid, etc.may be used.

Some dec'olorizing usually occurs during the hydrogenation process.

Where the treatment is with certain monohydric alcohols, such as butyl,benzyl, amyl alcohol, the treatment will involve heating the alcoholtogether with the reaction product under atmospheric pressure at asuitable temperature, say within the range C. to 225 C. 0n the otherhand, where the treatment is with a lower ali phatic alcohol, such asmethyl, ethyl alcohol, or the like, the treatment generally will involveheating at a suitable temperature, say within the range about 1507 -2500. under suitable pressure, for example, 200-1000 pounds, and where thetreatment is with a .polyhydric alcohol, as ethylene glycol, glycerol,sorbitol, pentaerythrite, etc., the treating will be at a temperature ofabout 200 C.275 C.

Many of the hydrogenated rosin compoundmaleic anhydride reactionproducts may be partially distilled under vacuum, say about. mm.pressure, making a preliminary cut to separate any unreacted reagentsand then distilled up to a bath temperature of about 300 C. making cutsif desired atabout 260 C. and 300 C. and leaving a residue. Either thedistillates or the residue may be hydrogenated and then, if desired;treated with alcohols.

In carrying out the method embodying this invention for the productionof the new resinous composition, it will be understood that the detailsof procedure given above are for purposes of illustration only and thatI do not contemplate limitation of my invention thereto, since variousmodifications in details of procedure may be made without departing frommy invention. It will also be understood that maleic acid may be reactedwith a reactive rosin compound instead of maleic anhydride.

This application is a continuation in part of application for U. S.patent of Irvin W. Humphrey, Serial No. 561,003, filed September 3, 1931(now United States Patent No. 2,025,947).

What I claim and desire to protect by Letters Patent is g 1. A reactionproduct of maleic anhydride with a reactive rosin compound having anarrangement of unsaturated chemical positions characteristic of rosinacids, the unsaturation of the product being reduced by hydrogen.

2. A reaction product of rosin and maleic anhydride, the unsaturation ofthe product being reduced by hydrogen.

3. A reaction product of abietic acid and maleic anhydride, theunsaturation of the product being reduced by hydrogen,

4. A reaction product of an ester of abietic acid and maleic anhydride,the unsaturation of the product being reduced by hydrogen.

5. A reaction product of a rosin acid ester and maleic anhydride, theunsaturation of the product being reduced by hydrogen.

6. A reaction product of a dihydric alcohol ester of abietic acid andmaleic anhydride, the unsaturation' of the product being reduced byhydrogen. 7. A reaction product of a polyhydric alcohol ester of abieticacid and maleic anhydride, the unsaturation of the product being reducedby hydrogen.

8. A reaction product of a glycerol ester of abietic acid and maleicanhydride, the unsaturation of the product being reduced by hydrogen.

9. The method of producing a synthetic resin, which includes reactingmaleic anhydride with a reactive rosin compound having an arrangement ofunsaturated positions characteristic of rosin acids and hydrcgenatingthe product.

10. The method of producing a synthetic resin, which includes reactingmaleic anhydride with a reactive rosin compound having an arrangement ofunsaturated positions characteristic of rosin acids, and hydrogenatingthe product under a pressure of about 200 to about 15,000 lbs. persquare inch in the presence of a base metal catalyst.

11. The method of producing a synthetic resin, which includes reacting arosin acid with maleic anhydride and hydrogenating the product.

12. The method of producing a synthetic resin, which includesreactingabietic acid with maleic anhydride and hydrogenating the product.

13. The method of producing a synthetic resin, which includes reactingan abietic acid ester with maleic anhydride and hydrogenating theproduct.

14. The method of producing a synthetic resin, which includes reacting adihydric alcohol ester of abietic acid with maleic anhydride andhydrogenating the product.

15. The method of producing a synthetic resin, which includes reacting apolyhydric alcohol ester of abietic acid with maleic anhydride andhydro- .genating the product.

16. A reaction product of a polyhydric alcohol ester of a rosin acid andmaleic anhydride, the unsaturation of the product being reduced byhydrogen.

17. The method of producing a synthetic resin which includes reactingglycerol abietate with maleic anhydride and hydrogenating the product.18. The method of producing a synthetic resin which includes reactingglycol abietate with maleic anhydride and hydrogenating the product.

19. A reaction product of glycol abietate and maleic anhydride, theunsaturation of the product being reduced by hydrogen.

IRVIN W. HUMPI-IREY.

